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United States Patent m

Kiistinsson

[i i] Patent Number: 4,996,325
[45] Date of Patent: Fein 26, 1991

[54] PESTICIDES

[75] Inventor: Haukur Kristiiisson, Basel,
Switzerland

[73] Assignee: Ciba*Geigy Corporation Ardsley,
RY.

[21] AppL No.: 492,704

[22] Filed; Mar. 13, 1990

Related U.S. Application Data

[62] Division of Ser, No, 255,684, Oct. 11, 1988, Pat. No.
4,931,439.

[3D] Foreign Application Priority Data

Oct 16, 1987 [CH] Switzerland 4C62/B7

[51] Int.CL* C07D 271/07

[52] U.S. 0 548/132

158] Field of Search 548/132

[56] References Cited

FOItJEIGN PATENT DOCUMENTS

17957S5 8/1975 Fed. Rep. of Germany .

OTHER PUBLICATIONS

A. Hetzhein et al t Liebigs Ann, Chem,, vol. 749, pp.
125-133 (1971).

Primary Examiner — John M, Ford

Attorney, Agent, or -Kevin T. Mansfield

[57] ABSTRACT

Novel substituted N-amino-l t 2,4-triazinones of formula

i

(I)

wherein

Ri is hydrogen, Ci-Cualkyl, Ca-Qcycloalkyl,
Ci^C4aIkoxy-Ci»C6alkyl T Ci~C 3 hatoalkyl t phenyl,
benzyl, phenethyl, phenpropyl* phenbuty! or phen-
pentyl, or a phenyl, benzyl, phenethyl, phenpropyl,
phenbutyl or phenpentyl radical that is mono* or
di-substituted by halogen, Ci-Csalkyl, C1-C2-
haioalkyl, methoxy and/or by ethoxy,
R2is hydrogen, Ct-Cealkyl or C3-C6cycloalkyl, or Is
phenyl that is unsubsthuted or substituted by
Cj-Ci2alkyl, halogen or by CH^haloalkyl, or Ri
and R2 together form a saturated or unsaturated 3-
to 7-membered carbocycle,
R3 is hydrogen or Ct-C^alkyl and
Z is — N^CH— or — NH — CH2 — ,
and their salts with organic or inorganic acids, pro-
cesses and intermediates for their preparation, and their
use in pest control and in pesticidal compositions that
contain a compound of formula I as active ingredient
are disclosed. The preferred field of application is the
control of pests in and on animals and plants.

4 Claims, No Drawings

4,996,325

PESTICIDES

This is a divisional of application Ser. No. 255,684
filed on Oct, 11, 1988 now U.S. Pat, No, 4,931,439.

The present invention relates to novel insecticidally
active N-amino-I,2,4-tnazinones, processes and inter-
mediates for their preparation, compositions containing
these aminotriazinones, and their use in pest control

The aminotriazmones according to the invention
corresponding to formula I

10

CD

IS

20

25

wherein

Ri is hydrogen, C1-C12 alkyl, C3-Qcycloalkyl,
■ Ci-C4~atkoxy-Ci-C6alkyU Ct-CahaloalkyU phenyl,
benzyl, phenethyl, phenpropyl, phenbutyl or phenpen-
tyl». or a phenyl, benzyl, phenethyl, phenpropyl, phen-
butyl or phenpentyl radical that is mono- or di-sub-
stituted by halogen, Ci-CsalkyI, Ci^haloalkyl, me-
thoxy and/or by etboxy,

R2is hydrogen, Cj-Cealkyl or C3~QcycloaIkyl T or is 30
phenyl that is unsubstituted or substituted by Ci-Cwal-
kyl, halogen or by Ci~Gnhaloalkyl, or Kt and R2 to-
gether form a saturated or unsaturated 3* or 7-mem-
bered carbocycle,

R3 is hydrogen or Ci -Chalky! and ^5
Z i s _N=-CH~ or r-NH — .
The compounds of formula I can also be in the form of
acid addition salts* Both organic and inorganic acids are
suitable for the formation of such salts- Examples of
such acids are t inter alia, hydrochloric acid, hydro-
bromic acid, nitric acid, various phosphoric acids, sulfu-
ric acid, acetic acid, propionic acid, butyric acid, valeric
acid, oxalic acid, malonic acid, maleic acid, fumaric
acid, lactic acid, tartaric acid or salicyclic acid.

The alkyl radicals that are suitable as substituents 45
may be straight-chained or branched. Examples of such
alkyl radicals are methyl, ethyl, propyl, isopropyl, bu-
tyl, isobutyl, sec-butyl, tert-butyl or pentyl hexyl, oc-
tyl, decyi, dodecyl, etc. and their isomers.

The alkoxyalkyl radicals that are suitable as substitu- 50
enf s may be straight-chained or branched, the alky! and
alkoxy radicals being as defined above* Suitable exam-
ples of such substituents are, inter alia, methoxymethyl,
methoxyethyt, ethoxyethyl, methoxypropyl, ethoxy-
propyi, propoxypropyl, methoxybutyl, ethoxybutyl, 55
propoxybutyl or butoxybutyl.

The cycloalkyl radicals that are suitable as substitu-
ents are, for example, cyclopropyl, cyclobutyl, cyclo-
pentyl or cyciohexyl.

The halogen atoms that are suitable as substituents 60
are fluorine and chlorine and also bromine and iodine,
fluorine and chlorine being preferred.

The halogenated C|-C2alkyt radicals that are suitable
as substituents may be only partially halogenated or
may be perhaiogenated, the halogen atoms being as 65
defined above. Especially suitable examples of such
substituents are, inter alia, methyl mono- to tri-sub-
stituted by fluorine, chlorine and/or by bromine, for

example CHFa or CF 3 ; and ethyl mono- to penta-sub-
stituted by fluorine, chlorine and/or by bromine, for
example, CH2CF3, CF 2 CF 3 ,- , CF a CCb, CF2CHCI2,
CF2CHF2, CF 2 CHBr 2 , CF2CHCIF, CF 2 CHBrF or
CC1FCHC1R

The 3- to 7-membered carbocycles formed by Ri and
Ra may be saturated or unsaturated. They are preferably
saturated 5- or 6-membered carbocycles.

Of the compounds of formula I, prominence should
be given to those wherein R] is hydrogen, Ct-Ceatkyl,
C3~C5cycloalkyl, phenyl or phenyl that is mono- or
di-substituted by halogen, Ci-C3alkyl, methoxy or by
ethoxy; each of R2 and R3 is hydrogen or Ci-C4aikyl
and Z is — N=CH— or -NH— CH 2 —

Of the above, the compounds of formula I that are
preferred are those wherein

(a) R\ is hydrogen, Ci-C4alkyl, cyclopropyl or
phenyl; R2 is hydrogen, methyl or ethyl; R3 is hydrogen
or methyl; and Z is — N=CH — or

(b) Rt is hydrogen, Ci~C4alkyl, cyclopropyl or
phenyl; Rats hydrogen, methyl or ethyl; R3 is hydrogen
or methyl; and Z is — NH — CHj — .

The compounds of formula I according to the inven-
tion can be prepared in accordance with processes that
are known in principle, for example by

(A) reacting an aminotriastnone of formula II

*3

NH 2

A

N

H

with an aldehyde of formula III

am

OCH-

and, if desired,

(B) converting the resulting
methy.eneamino-triazinone of formula la

Ra R 3

A

pyridyl-

da)

N
H

by selective reduction into the pyridyl-methylamino-
triazinone of formula lb

3

4,996,325

4

Ob)

R 2 (VI)
-C— CO—

I

&3

Ri t R2 and R3 being as defined for formula I and X being
halogen.

The process for the preparation of the oxadiazolones
10 of formula IV is carried out under norma! pressure in
„ « ■ _ A-r^+A the presence of a base and in a solvent The temperature

In the above formulae, R,, R2 and R3 are as defined fe ^ Qfl (o + ^ ^ preferably from +2 0* to 100* C

hereinbefore. Suitable bases are organic and inorganic bases, for ex-
Process A is generally carried out under normal pres- ample t n me thylarnine, aicoholates, sodium hydroxide
sure in the presence of a catalytic amount of a strong 15 ^ so ^ um hydride. Suitable solvents are, inter alia,
acid and in a solvent. The reaction temperature is from alcohols, halogenated hydrocarbons, for example chlo-
+ 10* to 100° C., preferably from +40" to 80' C Suit- reform, nitriles, for example acetonitrile, tetrahydrofu-
able acids are strong inorganic acids, for example mh> ran? ciioxane, dimethyl sulfoxide or, alternatively, wa~
era! acids, especially hydrochloric acid. Suitable sol- 2Q t er.

vents are alcohols, ethers and ethereal compounds, Of the aminotriazinones of formula II, 4-amino-6-phe-

nitriles or, alternatively, water, nyl-I A4-tria«in-3-one is known (Liebigs Annalen der

Process B is generally carried out under normal or Chemie, 749, 125 (1971)), that is to say, the compound
slightly elevated pressure in the presence of a suitable of formula II wherein Rife phenyl and each of R 2 and
hydrogenation catalyst and in a solvent. Suitable hydro- 25 R 3 is hydrogen All the other compounds of formula II,
gLtion catalysts are the customary platinum, palla- that is to say the compounds of formula Ha
dium or nickel catalysts, for example Raney nickel* or
also hydrides, for example sodium borohydride. Suit-
able solvents are alcohols, acetic acid, ethyl acetate or, 3(}
alternatively, water.

The aminotriazinones of formula II can be prepared,
for example, by a ring rearrangement using hydrazine
hydrate by reacting an oxadiazolone of formula IV

35

(Ha)

R 7 R 3 (IV) , .

\ / wherein

c-CO— Ri R t ' is hydrogen, Cj-Cnaikyl, Cj-Cecycloalkyl,

Ci-C4alkoxy-Ci^C6aikyl, Ci-C2haloalkyl, benzyl,

, v ^0 phenethyl, phenpropyl, phenbutyl or phenpentyl, or a

CF 3 — ^ >=o phenyl, benzyl, phenethvl, phenpropyl, phenbutyl or

\ / phenpentyl radical that is mono- or di-substituted by

o halogen, C^C 5 alkyl, Ci~€2-haloalkyl f methoxy and/or

by ethoxy,

with hydrazine hydrate (H 2 N-NH 2 .H20), R,, K 2 and 45 K 2 is hydrogen, Ci-C«alkyl or Cj-Qjcycloalkyl , or is
R 3 being as defined for formula L phenyl that is unsubstituted or substituted by Cj-Curf-

The Loess for the preparation of the aminotriazi- kyi, halogen or by C^CnhaloalkyU or Ri and R 2 to-
1 ne process tor uic P«p*«« aether form a saturated or unsaturated 3- to 7-mem-

nones of formula II is generally carried out under nor* ^red carb^cycle

mal pressure and, if desired, in a solvent The tempera- 50 R ^ fe h drogen or C ,-C6alkyl, and the oxadiazolones
ture is from + 15* to 120" C, preferably from +20 to Qf formu|a 1V are novd and the invention relates also to
80" C. Suitable solvents are, inter alia, water, nitriles,

such as acetonitrile, alcohols, dioxane or tetrahydrofu- The compoun< i s 0 f formulae 1X1, V and VI are known
ran. t 5$ or can be prepared in accordance with processes that

The oxadiazolones of formula IV can be prepared in are ^own in principle,
accordance with processes that are Joiown in principle, xt has been found that the compounds of the formula
for example by reacting the 5-trifluoromethyM,3,4- 1 according to the invention, at the same time as being
oxadiazol-.2<3H)-one of formula V well tolerated by plants, are better tolerated by warm-

6Q blooded animals and have a greater stability than

N — n

m known phosphoric acid esters and carbamates. They are
therefore eminently suitable as pesticides, especially for

controlling pests t especially insects, that attack plants
*f y*=° and animals.

\ / 65 The compounds of formula I are suitable especially

o for controlling insects of the orders Lepidoptera, Cole-

opiera, Homoptera, Heteroptera, Diptera, Thysanopt-
with a ketone of formula VI era, Orthoptera, Anoplura, Siphonaptera, Mallophaga,

4,996,325

5 6

Thysanura, Isoptera, Fsocoptera an&Hymenoptera and broken brick, sepiolite or bentomte; and suitable non-
also representatives of the order Acarina, sorbent carriers are, for example, calcite or sand. In

With the aid of the compounds of formula I used addition, a great number of granulated materials ot
according to the invention it is possible to control espe- inorganic or organic nature can be used, e.g. especially
ciaiiy plant-destructive insects, especially plant-destruc- 5 dolomite or pulverised plant residues,
tive insects in crops of ornamental and useful plants, Depending on the nature of the compound of formula
especially in cotton crops, vegetable crops, rice crops I to be formulated, or on the nature of the combinations
and fruit crops. In this connection, attention is drawn to thereof with other insecticides or acancides, suitable
the fact that the said 'compounds are distinguished both surface^active compounds are non-iomc f cationic and-
by a very pronounced systemic action and also contact 10 /or anionic surfactants having good emulsifying, dis-
action against sucking insects, especially against insects persing and wetting properties. The term ; surfactants
of the Aphididae family (for example Aphis fabae, Aphis will also be understood as comprising mixtures of sur-
craccivora and Myzus persicae) that can be controlled by factants.

conventional pesticides only with difficulty. Both so-called water-soluble soaps and also water-

The good pesticidal activity of the compounds of 15 soluble synthetic surface-active compounds are suitable

formula I proposed according to the invention corre- anionic surfactants.

sponds to a mortality of at least from 50 to 60 % of the Suitable soaps are the alkali metal salts, alkaline earth
pests mentioned, metaI salts or ansubstituted or substituted ammonium

The activity of the compounds used according to the salts of higher fatty acids (C10-C22), e.g. the sodium or
invention or of the compositions containing them can be 20 potassium salts of oleic or stearic acid, or of natural
substantially broadened and adapted to prevailing cir* fatty acid mixtures which can be obtained e.g. from
cumstances by adding other insecticides and/or acari- coconut oil or tall oil Other suitable surfactants that
cides. Suitable additives are, for example, representa- may be mentioned are fatty acid methyltaunn salts and
tives of the following classes of active ingredient: or- modified and unmodified phospholipids, ^
ganophosphorus compounds, nitrophenols and deriva- 25 More frequently, however, so-called synthetic sur-
tives thereof, formamidines, ureas, carbamates, pyre- factants are used, especially fatty sulfonates, fatty su -
throids, chlorinated hydrocarbons and Bacillus thurin- fates, sulfonated benzimidazole derivatives or alkylaryl-
giensis preparations, sulfonates.

The compounds of formula I are used as pesticides in The fatty sulfonates or sulfates are usually m the form
unmodified form or, preferably, together with the adju* 30 of alkali metal salts, alkaline earth metal salts or unsub-
vants conventionally employed in the art of formula- stituted or substituted ammonium salts and generally
tion, and are therefore formulated in known manner e.g. contain a C 8 -C 2 zalkyl radical which also includes the
into emulsifiable concentrates, directly sprayable or alkyl moiety of acyl radicals, e.g, the sodium or calcium
dilutable solutions, dilute emulsions, wettable powders, salt of lignosulfonic acid, of dodecyisulfate or of a mix-
soluble powders, dusts, granulates, and also encapsula^ 35 ture of fatty alcohol sulfates obtained from natural fatty
tions in e.g. polymer substances. As with the coraposi- acids. These compounds also compose the slats of suc-
tions, the methods of application, such as spraying, fated and sulfonated fatty alcohol/ethylene oxide ad-
atomising, dusting, scattering or pouring, are chosen in ducts. The sulfonated benzimidazoie derivatives prefer-
accordance with the intended objectives and the pre- ably contain 2 sulfonic acid groups and one fatty acid
vailing circumstances. ' ^> radical containing about S to 22 carbon atoms. Exam-

The formulations, Le, the composition, preparations pies of alkylarylsulfonates are the sodium, calcium or
or mixtures containing the compound (active ingredi-* triethano! amine salts of dodecylbenzenesulfomc acid,
ent) of "formula I or combinations thereof with other dibutylaaphthalercesulfonic acid, or of a condensate of
insecticides or acaricides and, where appropriate, a naphthalene-sulfonic acid and formaldehyde. Also suit-
solid or liquid adjuvant, are prepared in known manner, 45 able are corresponding phosphates, e.g. salts of the
e.g. by homogeneously mixing and/or grinding the phosphoric acid ester of an adduct of p-nonylphenol
active ingredients with extenders, e.g. solvents, solid with 4 to 14 moles of ethylene oxide,
carriers and, where appropriate, surface-active com- Non-ionic surfactants are preferably polyglycol ether
pounds (surfactants). derivatives of aliphatic or cycloatiphatic alcohols, satu-

Suitable solvents are; aromatic hydrocarbons, prefer- 50 rated or unsaturated fatty acids and alkylpheaols, said
ably the fractions containing 8 to 12 carbon atoms, e.g. derivatives containing 3 to 30 glycol ether groups and
xylene mixtures or substituted naphthalenes, phthalates, 8 to 20 carbon atoms in the (aliphatic) hydrocarbon
such as dibutyl phthalate or dioctyl phthalate, aliphatic moiety and 6 to IS carbon atoms m the alkyl motety of
hydrocarbons, such as cyclohexane or paraffins, alec- the aikylphenols. Further suitable non-ionic surfactants
hols and glycols and their ethers and esters, such as 55 are the water-soluble adducts of polyethylene oxide
ethanol, ethylene glycol, ethylene glycol monomethyl with polypropylene glycol, ethylenediammopolypropy-
or monoethyl ether, ketones, such as cyclohexanone, kne glycol and alky Ipoly propylene glycol containing 1
strongly polar solvents, such as N^methyl~2-pyrroii- to 10 carbon atoms in the alkyl chain, which adducts
done, dimethyl sulfoxide or dimethylformamide, as well contains 20 to 250 ethylene glycol ether groups and 10
as vegetable oils or epoxidised vegetable oils, such as 60 to 100 propylene glycol ether groups. These com-
epoxidised coconut oil or soybean oil; or water. pounds usually contain 1 to 5 ethylene glycol units per

The solid carriers used e.g. for dusts and dispersible propylene glycol unit,
powders are normally natural mineral fillers, such as Representative examples of non-ionic surfactants are
calcite, talcum, kaolin, moritmoriilonite or attapulgite. nonylphenolpolyethoxyethanols, caster oil polyglycol
In order to improve the physical properties it is also 65 ethers, polypropylene/polyethylene oxide adducts,
possible to add highly dispersed silicic acids or highly tributylphenoxypolyethoxyethanol, polyethylene gly-
dispersed absorbent polymers. Suitable granulated ad- col and octylphenoxypolyethoxyethanol. Fatty acid
sorptive carriers are porous types, for example pumice, esters of polyoxyethylene sorbttan, e.g. polyoxyethyl-

4,996,325

10

20

ene sorbitan trioleate, are also suitable non-ionic surfac-
tants.

Cationic surfactants are preferably quanternary am-
monium salts which contain, as N-substituent, at least
one Ca-Cs&alkyl radical and, as further substituents,
unsubstituted or halogenated lower alky], benzyl or
hydroxy-lower alkyl radicals. The salts are preferably
in the form of hahdes, methyl sulfates or ethyl sulfates,
e,g. stearyltrimethylamtnonium chloride or benzyldi(2-
chloroethyI)ethylammonium bromide.

The surfactants customarily employed in the art of
formulation are described, inter alia, in the following
publications:

15

*'Mc Cutcheon's Detergents and Emulsifiers An-
nual** MC Publishing Corp,, Rldgewood, N.J. r
1979; Dr. Helmut Stache "Tenside Taschenbuch",
Carl Hanser Verlag, Munich/Vienna 198L
The pesticsdai compositions according to the inven-
tion usually contain 0.1 to 99 %, preferably 0.1 to 95 % t
of a compound of formula I or combinations thereof
with other insecticides or acaricides, I to 99,9 % of a
soiid or liquid adjuvant, and 0 to 25 %, preferably 0,1 to
20 % f of a surfactant. Whereas commercial products 25
will preferably be formulated as concentrates, the end
user will normally employ dilute formulations contain-
ing substantially lower concentrations of active ingredi-
ent.

The compositions according to the invention may 30
also contain further additives such as stabilisers, anti-
foams, viscosity regulators, binders and tackifiers as
well as fertilisers or other active ingredients for obtain-
ing special effects. 35

EXAMPLES

L Preparation of the compounds of formula I and their
intermediates

Example P.l: 40
2-oxo-5~trifluoromethyl-2,3-dihy dro- 1 , 3 f 4-oxadiazol»
3 -acetone

15 g (0,5 mole) of 80 % NaH dispersion in oil are
washed free of oil with petroleum ether and added to ^
125 ml of DMR 77 g (0,5 mole) of 5-tri0uoromethyl-
l3,4-oxadiazol-2(3H)-one in 250 ml of DMF are added
dropwise to this suspension over a period of 1 hour at
room temperature and the batch is then stirred for 3
hours, 55.5 g (0*6 mole) of chloroacetone are then added
and the reaction mixture is stirred for 16 hours at room
temperature. After concentration by evaporation, 1000
ml of water are added to the residue and the solid pre-
cipitate is filtered off with suction and dried to give the
title compound of formula 55

8

TABLE 1

c

/

CH 2 — -CO— CHj

(compound no, U.)

!=0

jound no.

&2

R3

physic, data

U

CH3

H

K

m.p. 85 c C.

1,2

H

H

m.p. 74-75* C.

1.3

C(CH 3 h

H

H

m,p. 6V C.

1.4

C 6 H 5

H

H

m.p, 100-102* C.

1.5

CH 3

CH3

H

oil

1.6

CH 3

CH3

CH3

Oil

1.7

C2H5

H

H

m.p. 76-77* C.

LS

H

H

m.p. 77-78* C.

H

H

H

C2H5

H

n.C 3 K 7

H

H

H

j-C 3 H 7
C(CH 3 )3
CH3
CH3

CHj

CH3
CH3
CH3
CH3
C2H5
C2H5

H

H
CHj

H

H
CH3

CH 3 CH3

C2H5 CH3

Example P.2:
2,3,4, 5-tetrahydro-3-oxo-4"amtno-6-methyl~ 1 ,2,4-tria-
zine

210 g (1.0 mole) of 2-oxo»5»trifluoromethyl-2,3-dihy-
dro-I^Aoxadiazol-S-acetone are introduced, with
cooling, into 250 ml of hydrazine hydrate. The resulting
clear brown solution is concentrated by evaporation in
vacuo after being stirred for 2 hours and the residue is
chromatographed on silica gel (methylene chloride/me-
thanol 9:1), The solvent is evaporated off and the title
compound of formula

CH3

60

(compound no. 2A.)

N
H

in the form of a colourless solid; m.p. 85° O; yield: 96 g 65 crystallises from the resulting oil after the addition of

(91/7 %). ether; m.p. 117 fl -119 0 C.; yield: 64 g (50 %).

The following compounds are prepared in an anlo- The following compounds are prepared in an analo-
gous manner: gous manner:

9

TABLE 2

4,996,325

10

TABLE 3

Ra Rj

Compound no.

Ri

R2

R3

m-p, *C

2,t

CHj

H

H

U7-II9

2.2

CHj

CH3

H

172-174

2-3

CH3

CH3

CHj

138-139

2.4

QH 5

H

H

143*145

2.5

H

H

79-8!

2.6

C(CH 3 )3

H

H

143-150

2.7

H

H

9-^-95

2,8

C6H 5

H

H

199-202

4-CJ— CfiH*

H

H

208-2 IG

H

H

H

CH 3

C2H5

H

C 2 H 5

CH 3

CH 3

C 2 H 3

CH3

H

11-C3H7

H

H

1VC3H7 1

CH 3

H

CH3

CH 3

1-C3K7

CH3

H

CCCH 3 > 3

CH3

H

CH 3

CH 3

CH3

CHj

CH 3

H

10

15

20

25

30

35

N=CH'

40

Example P.3:
2,3 T 4 t 5-tetrahydro-3-oxo-4-[(pyndine-3-yI)-
xiiethyl«neamtno]-6-methyl-i,2,4-triazine

26*8 g (0*25 mole) of pyridine-3-carbaldehyde and 1
drop of concentrated HC1 are added at 60* C* to 32 g
(0.25 mole) of 2 t 3 ) 4,5-tetrahydro»3-oxo-4~amino-6-
methyl-l,2*4-triazine dissolved in 250 ml of etfaanol,
After boiling for half an hour under reflux, the reaction
mixture is cooled and the solid portion is isolated by
filtration, washed with ether and dried to give the title
compound of formula

CH3

N— CH-

(compound no, 3.1.)

45

50

SS

Com pound no.

Ri

R2

Rj

physical data

3.1

CK3

H

H

rrirPr

227-228* C.

3.2

CH3

CH3

H

rn,p-

139-14!° C.

3.3

CH3

CHj

CK3

rn,p.

3.4

H

H

m.p.

223-224' C.

3.5

UC3H7

H

H

201-203* C.

3.6

H

H

m.p.

243-244' c.

3.7

C(CH 3 ) 3

H

H

m.p.

195-196° C

3.8

C 6 H 5

H

H

m,p*

263-264* C.

3,9

4-CI—C6H4

H

H

ro-p-

246-247* C.

H

H

H

CH 3

H

H

CH3

CH3

CH3

CaHj

H

CH3

C 2 H 5

CH3

CH 3

C 2 H 5

C 2 H 5

CH3

H

C 2 H 5

CH3

CH 3

CaH S

C3H5

H

n-C 3 H 7

H

H

n-C 3 H7

CH3

H

n-C3H7

CH 3

CH 3

J1-C3H7

C2H5

CH 3

I-C3H7

CH 3

H

UC3H7

CH3

CH 3

/\

CH 3

H

CH 3

CH 3

C(CH3) 3

CH 3

H

C<CH 3 ) 3

CH3

CH 3

11-C4H9

H

H

C6H5

CH3

H

C6H5

CH 3

CHj

N
H

in the form of a colourless solid; roup* 227°-228'
yield; 4g g (90 %).

The following compounds are prepared in an analo-
gous manner:

60

C; 65

Example P.4:

2 f 3,4,5-tetrahydro-3-oxo-{(pyridin-3-yl)-methyiamino]-
6-isopropyl- 1 ,2»4~triazine

37.8 g (1 mole) of sodium borohydrideare introduced
in portions into a suspension of 24.5 g (0,1 mole) of
2,3 t 4,5-tetrahydro*3-oxo-4-[(pyridin-3-yl)-
methyleneamino]-6-isopropyl-l,2,4-triazine in 800 ml of
methanol; the reaction mixture is then stirred for a few
hours at room temperature and then boiled under reflux
for 12 hours. After evaporation of the solvent, the resi-
due is stirred with acetonitrile and then filtration is
carried out. After concentration the acetonitrile solu-
tion by evaporation, the residue is stirred with ether and
the crystaUisaie is isolated by filtration to give the title
compound of formula

11

4,996,325

12

(compound no. 4, i .)

<CH2)?.CH

/

NH— CH 2 -

■a_>

CH3

\

A

N
H

in the form of a colourless crystal powder; m,p.
lOSMOT C; yield: 12 g (49 %),

The following compounds are prepared in an analo-
gous manner:

TABLE 4

15

NHCHy

N
H

N \ A.

* ,„■» {compound no. 5.!.}

N=C ""V /"

.HCl

10

N
H

in the form of a colourless crystal powder; m.p,
240*-24P C. with decomposition; yield: 19 g {75 %).

The following compounds are prepared in an analo-
gous manner:

TABLE 5

20

25

*2

\

R3

H

h ye

Compound no.

Rl

*2

physical data

4J

i-C 3 H 7

H

H

m,p. 105-107* G.

4.2

CHj

R

H

m,p. 161-163" C

4,3

C{CH 3 ) 3

H

H

m.p. 162-164° C

4.4

Cj.Hs

B

H

m.p. 94-96* C.

4.5

A.

H

H

m.p. 133-135* C,

4,6

CH 3

CH 3

H

ra.p. 35' C,

4,7

CH 3

CH 3

CH3

m.p. ISO 11 C,

H

H

H

H

CHj

H

C 2 H 5

CH3

H

n-CjHy

H

H

i-CjK 7

CH3

H

i-CjH?

CH 3

CH3

A^

CH3

H

A

C2H5

CH 3

C(CH 3 } 3

CH3

H

C(CH 3 b

CH3

C(CH 3 )j

C 3 H 5

H

C 6 H S

H

H

C6H 5

CH3

H

30

35

40

45

SO

55

60

Example P.Sr
2 t 3,4 f 5«tetrahydro-3«oxo-4-[(pyndm-3-yl)>-
methyleneamino]-6-methyl-U2,4-tnazinehydrochloride

2L7 g of 2,3,4 7 5-tetrahydro-3-oxo-4-[(pyridin"3-yl)»
methyleneamino]'6'methyl-l J 2 1 4"triazine are dissolved,
with heating, in 60 mi of 2N hydrochloride acid. The
hot solution is filtered and cooled. The precipitate 55
which crystallises out is isolated by filtration* washed
with alcohol and ether and dried in vacuo to give the
title compound of formula

Com-

pound

m,p.

no.

R2

R 3

Z

Y e

•c.

5.1

CH3

H

H

— N=CH~~

CI

240-
241

5.2

CHj

H

H

hSOi

237

5.3

C2H5

H

H

CI

253

5.4

C 2 H 5

H

H

205

5,5

C2H5

H

H

~n— ch~

N0 3

181

5,6

CH 3

H

H

— N=CH~-

NO3

177

5.7

C2H5

H

H

— N=CH—

CH 3 S0 3

224-.
225

5.S

CH3

H

H

~N— CH—

CF3CO2

196

5.9

CH 3

H

H

— N^=CH—

206-
210

5.10

CH3

H

H

— N«aCH—

oxalic
acid

21S-
219

5,11

{CHj) 3 C

H

H

— Nb=*CH—

Ci

229™
230

5.12

.As.

H

H

— N=CK—

NO3

229-
230

5.13

A

H

H

— N=CH—

CI

250

5.15

5.16

5,17

H H — N—CH—

H H — N=CH-

CFjCOa 196-
198

H H

-N—CH-

ojcalic
acid

hSO A

H H N=CH— APO4

220

210

219

13

4,996,325

14

2. Formulation Examples

Formulations for active ingredients of formula I or
combinations of these active ingredients with other
insecticides or acaricides (throughout, percentages are 5
by weight):

Fl. Wettable powders

(a)

<<s)

active ingredient or combination

25%

50%

75%

sodium Hgnosulfonate

5%

5%

sodium \mry\ sulfate

3%

5%

sodium diisobutylnaphthalene*

6%

10%

sulfonate

octylphenol polyethylene glycol

2%

ether (7-8 males of ethylene oxide)

highly dispersed silicic acid

5%

10%

10%

kaolin

62%

27%

The active ingredient or combination is mixed with the
adjuvants and the mixtures is thoroughly ground in a 20
suitable mill, affording wettable powders which can be
diluted with water to give suspensions of the desired
concentration.

F2. Emulsifiable concentrate

active ingredient or combination

10%

octylphenol polyethylene glycol

3%

ether (4-5 mole* of ethylene oxide)

calcium dodecylbenzenesulfonate

3%

castor oil poly&lycol ether

4%

(36 moles of ethylene oxide)

cyclohexanone

30%

xylene mixture

50%

Emulsions of any required concentration can be ob- 35
tained from this concentrate by dilution with water.

F3. Dusts -

<«)

active ingredient or combination

5%

8%

talcum

95%

kaolin

92%

Ready-for-use dusts are obtained by mixing the active

ingredient or combination with the carrier and grinding

the mixture in a suitable mill.

F4. Extruder granulate

active ingredient or combination

10%

sodium iignosultonate

2%

carboxymethylceHulose

\%

kaolin

37%

40

45

50

the active ingredient or combination is mixed and
ground with the adjuvants, and the mixture is subse- 53
quently moistened with water. The mixture is extruded,
granulated and then dried in a stream of air,

F5. Coated granulate gO

active ingredient or combination 3%

polyethylene glycol (mot wt. 200) 3%

kaolin 94%

The finely ground active ingredient or combination is 65
uniformly applied, in a mixer, to the kaolin moistened
with polyethylene glycoL Non-dusty coated granulates
are obtained in this manner,

F6, Suspension concentrate

active ingredient or combination

40%

ethylene glycol

10%

nonyiphenol polyethylene glycol

6%

ether (1$ moles of ethylene axitfe)

sodium Hgnosulfonate

10%

carboxymet hyl cfcl f « lose

1%

37% aqueous formaldehyde solution

0.2%

silicone oil in the form of a 75%

aqueous emulsion

0.8%

water

32%

The finely ground active ingredient or combination is
intimately mixed with the adjuvants, giving a suspen-
sion concentrate from which suspensions of any desired
concentration can be obtained by dilution with water.

3, Biological Examples
Example B.I: Action against Aedes aegypti (larvae)

A concentration of 400 ppm is obtained by pipetting
a specific amount of a 0, 1 % solution of the test com-
pound in acetone onto the surface of 150 ml of water in
a container. After the acetone has evaporated, 30 to 40
two-day-old Aedes larvae are put into the container.
Mortality counts are made after 2 and 7 days.

Compounds according to Examples P.3 to P.5 exhibit
good activity in this test.

Example B,2: Contact action against Aphis craccivora

Before the start of the test, 4- to 5-day-old pea seed-
lings (Vicia faba) reared in pots are each popoulated
with about 200 insects of the species Aphis craccivora.
The treated plants are sprayed direct to drip point 24
hours later with an aqueous formulation containing 12.5
ppm of the test compound. Two plants are used for each
test compound, and a mortality count is made after a
further 24 and 72 hours. The test is carried out at
21V22* C and a relative humidity of about 55 %.

Compounds according to Examples P.3 to P. 5 exhibit
good activity in this test.

Example B.3: Systemic action against Aphis craccivora

Rooted bean plants are transplanted into pots con-
taining 600 ccm of soil. 50 ml of a formulation (prepared
from a 25 % wettable powder) of the test compound in
a concentration of 400 ppm are then poured directly
onto the soil in each pot

After 24 hours the growing parts of the plants are
populated with aphids of the species Aphis craccivora
and a plastic cylinder is then slipped over the plants to
protect the aphids from any passible contact with the
test substance either directly or via the gas phase,

A mortality count is made 48 and 72 hours after the
start of the test Two plants, each in a separate pot, are
used for each test substance. The test is carried out at
25* C. and the 70 % relative humidity.

Compounds according to Examples P.3 to P.5 exhibit
good activity in this test.

Example B:4. Contact action against Myzus persicae,
direct spray test

4 days before treatment, peperoni plants (in the 6-Ieaf
stage, in pots) are infested with a population of Myzus
persicae (R strain) by placing pea seedlings 2-3 cm long
and well populated with aphids on the peperoni plants.
As soon as the pea seedlings begin to dry up, the aphids
migrate onto the test plants (peperoni). 24 hours later.

IS

4,996,325

the treated plants are sprayed direct to drip point with
an aqueous suspension, prepared from a 25 % wettable
powder* containing 100 ppm of the test compound.
Four plants are used for each test substance, A mortal-
ity count is made 7 days after application. The test is
carried out at 2V-22* C. and about 60 % relative hu-
midity.

The compounds according to Examples P.3 to P. 5
exhibit 80-100 % mortality in this test

Example Test of long-term action against Myzus
persicae

Peperoni plants (in the 6-leaf stage, in pots) are
treated by spray application with the test solutions and,
2 days after the treatment, the test plants are infested
with a population of My2us persicae {R strain) as de-
scribed in Example B.4. An evaluation of the percent-
age mortality is made 5 days after populating the plants.

The compounds according to Examples P.3 to P,5
exhibit 50-100 % mortality at a concentration of 100
ppm.

What is claimed is;

1. Compounds of formula IV

10

15

20

25

C— CO— Ri

N—N

av)

30

35

40

wherein

Rj is hydrogen, Ci-Ctaalkyi, Cs-Cscycloalkyl,
Cj-G4alkoxy-Ci-C6aikylf Ci-C2haloalkyl t phenyl,
benzyl, phertethyl, phenpropyl, phenbutyl or phen*
pentyl, or a phenyl, benzyl, phenethyl, phenpropyi, 45
phenbutyl or phenpentyl radical that is mono- or
di-substituted by halogen, Cj-Cjalkyl, Ci-Cz*
haloalkyl, methoxy and/or by ethoxy,

R2 is hydrogen, Ct-C$alkyl or Ca-C^cycloalkyi, or is
phenyl that is unsubstituted or substituted by
Ci-Cnalkyl, halogen or by Ct-Cuhaloalkyl, or R\
and K.2 together form a saturated or unsaturated 3-
to 7-membered carbocycle* and

R3 is hydrogen or Ci-Csalkyt

2, Compounds of formula IV according to claim 1,
wherein Ri is hydrogen, Ci-C^alkyl, Cs-Cjcycloalkyi,
phenyl or phenyl that is mono- or di-substituted by
halogen, Ci-C^alkyl, methoxy or by ethoxy; and each
of R2 and R3 is hydrogen or C1-G4 alkyl,

3, Compounds of formula IV according to claim 2,
wherein Ri is hydrogen, C1-C4 alkyl or cyclopropyl;
R2 is hydrogen, methyl or ethyl; and R3 is hydrogen or
methyL

4, The compounds according to claim 3 of formulae

50

55

60

65

16

o
ii

CH 3 — C-CH3

N—N

N — N

O
11

CH 2 — C~ CH(CH 3 ) 2

CF 3 — ^)*=0

N—N

o

II

CH Z —C— C(CHj h

NF — N

o ^

CH 3 O
\ It

CH—C—CH3

N— N

CH3 CHj O

\ / II

C C— CH 3

N— N

o

/

CH 5 — C— C2H5

N — N

and

O
II

N—N

*****